Polymerization method



March 17, 1942. n. l.. GIBB POLYMERIZATION METHOD Filed Deo.*13, 1959 Y @SEG Petented Mar. 17, i942 4 onnraarzarron rmrnon nowancibmmmandmemmimnrmm Dow Chemical Co mpany, Midland, Mich., a

corporation oi Michigan d Y Application December 13, 1939, SerlaiNo. 308,992

z claims (ci. '1s-55) l'his invention concerns an improved method for polymerizing unsaturatedorganic compounds toproduce directly rodsor etc.. of the polymer in a form substantially free of ilaws and of any desired length.

The unsaturated organic compounds used as starting materials are those which are readily polymeriz'ed by heat to form solid glass-like j resins. In most instances. they are acrylic or vinyl compounds, e. g. methyl methacrylate, ethyl methacrylate, propyl methacrylate. vinyl acetate, vinyl butyrate, and vinyl aromatic compounds, such as styrene, ortho-chlorofstyrene, meta-chloro styrene, para-chloro styrene, parabromo styrene, ortho-methyl styrene,

styrene, para-ethyl styrene', diethyl styrene, paraisopropyl styrene, divnyl benzene, vinyl naph- -thalene, etc. The invention is particularly concerned with production of rods, bars, andthe like of the polymerized' viny1 aromatic compounds, which polymers are hereinafter referred to generically as vinyl aromatic resins.

' Itisknown-that such polymerizable compounds I contract in volume during polymerization and cooling and that :the vshrinkage often causes bubbles or other -aws in the polymerzed` products. The tendency toward bubble formation becomes more pronounced as the size of the articles to be produced is increased, and bubbles4 fre- -quently occurl in articles having a thickness or diameter greater than 0.5 inch when such articles are produced by the usual thermal polymeriza-V tion of the starting material in a mold.

The difficulty of polymerizing vinyl compounds in a mold to produce directly flawless articles has been recognized -in the art, and a nlnnber of c methods for carrying out the polymerization so as to .avoid the flaws due to shrinkage have been proposed. These previously known methods appear to involve a common `principle; viz., the material should be polymerized in a thin layer or as izablej' starting material containing a polymery ization catalyst in diminishing concentrations,

and then heating the charge to effect polymerization.

f these previously known methods, only that over a considerable part, e. g. d feet or more,

disclosed in U. s. Patent No. 2,057,513 is adapted to the production of iiawless rods of indefinite length, and the method of this patent involves certain operating diiiiculties. according to the patent, a rod of indeiinite length is prepared by iirst plugging one end of va horizontal tubular mold with the polymeric product, charging the remainder of the mold with the monomer under moderate pressure and then applying heat to a 'i0 narrow zone at the closed end of themold until polymerization in that zone is Icompleted, and progressively advancing the heating zone alongthe major axis of the mold at the rate required to eaect polymerizaumwnne iimintaining` the y meta-f 1'5 liquid in advance of the heating zone suiliciently methyl styrene, ortho-ethyl styrene, meta-ethyl cool to prevent active polymerization, After polymerizing the entire charge insuch manner,

` the inold and its contents are cooled, the rod of polymeric material is partially withdrawn, the

mold is recharged with monomeric material, and

polymerization 'as just described is repeated. This method is disadvantag'eous from a manufaeturing viewpoint in that it requires both positive heating and positive cooling during polymer' I ization with very careful control of the tempera-v tures and the rate of advance of the narrow heating zone, and it fln'ther requires the extra steps of periodically ceasing] polymerization and cooling the entire body ci' polymer to shrink it from the walls of the mold and permit its withdrawal 'so that the Imold may be reillled and polymerization be continued. Y' l It is an object of this invention to providea relatively simple method, free from the above` mentioned operating d iillculties, for the production of lawless-rods, bars, or similar articles of any, desiredlength.-

I have discovered that in the production of v finished rods, etc., by polymerizing an organic 4 compound in a mold, the occurrence of flaws of.

thetype caused by shrinkage may be avoided merely by gradually advancing the iilled mold into and through a heated zone to cause polymerization while charging the liquid to be polyvmerized into the mold 'at a pressuresuiiicient to compress the polymerizing material into a comvpact uniform vmass and thus to overcome the shrinkage which occurs. When operating in suchA manner, no cooling other than that dueto radiation isrequired (although, cooling may, if desired, be resorted to), and the heating need not be confined to a narrow zone, but may be extended overI as great a portion of the molds length as desired. By extending the zone of heatthe heating to an advancing narrow zone, the time required for polymerizing a given length of rod is shortened.

I also have devised a simple method which permits the continuous polymerization of a vinyl compound to producebubble-free rods or bars of as great length as desired.

'I'he accompanying drawing shows apparatus suitable for use in practicing the invention. Fig. 1 of the drawing is a side view of the apparatus; Fig. 2 is a cross-sectional end view of the section indicated as ,AA in Fig. 1; and Fig. 3 is a top cross-sectional view of the abutting ends of two sections of a mold. In Fig. 1, the numeral I designates an oven, which is heated by any conventional means, not shown. The'numeral 2 indicates a non-movable piston having a central bore 3 which permits the passage of liquid therethrough. Piston 2 is connected with a hollow shaft or conduit 4 which is supported by a wall or other supporting member l. Conduit 4 connects with pump 5 which in turn is connected by conduit G with a reservoir not shown. Encompassing piston 2 and extending through oven I is tubular mold 8 which consists of an assemblage of individual mold parts 8-a and 8-b. The mold rests upon and is capable of moving lengthwise on a supporting track I3. A brake assemblage is prcvidedto impede movement of mold 8 along track I3 in the direction away from piston 2 and at the same time to maintain a pressure on liquid within the mold. The brake assemblage consists of a brake cable 9, its supporting cable drums Il and I2, and a weight I attached to one end of the cable. The other end of the cable is iixed to one of the drums over which it passes and the mold 8 is clamped or otherwise attached to the cable at one or more points.

In Fig. 2, the numeral I a designates the wall of oven I. 8-a'is an upper half and 8-b a lower half of mold 8. Each'half is provided with the projecting lips I and I6, respectively, which lips are drilled forvpassage of the connecting bolts I'I therethrough. The lower half of the mold, 8-b, is provided with a cable-gripping member I4. The latter is provided with rollers 20 which rest on track I3 and support the mold on the track. Member I4 grips the cable 9 as indicated in the drawing.

In Fig. 3 of the drawing, adjoining lengths of the tubular mold are designated by the numeral 8-,b. Each mold length is provided vat its end with a circular ange I8, which is drilled with belt holes. flanges I8 draw theadjoining mold lengths together, thus forming a single tube.

In manufacturing a rod of polystyrene with the apparatus shown in the drawing, a length of the tubular molding is assembled and closed at one end with a metal capuor preferably a plug of solid polystyrene. The length of molding is placed on track I3 in such position as to have theA piston 2 and conduit 4 projecting therein through the open end of the mold to a point at .which the face of piston 2 ts snugly against the cap-or plug at the other end of the mold. `The lengthof molding is then anchored firmly to the brake cable 9 by means of the clamps I4.

Oven I is heated to a temperature suflcient to cause smooth, but fairly rapid, polymerization of styrene, e. g. usuallyto a temperature between The bolts I9 passing through the 2,276,69'1 'df' the length of the mold, instead of @cunning or other reservoir into the mold by means of the inlet 6, pump 5, conduit 4 and the bore 3 in piston 2. This introduction of liquid styrene into the mold through the bore of the stationary piston 3 forces mold 8 to move to the left along track I3 against the restraining force of brake cable 9 and weight I0, thus maintaining the styrene in the mold under considerable pressure. preferably under a pressure between and 250 pounds per square inch. The pressure exerted on the charge within the mold is dependent upon the weight I0 attached to cable 9 and may be varied, if desired, by changing that weight. The rate at which liquid styrene is pumped into the mold (and that the latter is thereby caused to move to the left through oven I) may be varied considerably, the optimum rate being dependent upon a number of variable factors, such as the rate of polymerization which in turn is dependent in part upon the temperature of the oven; the distance the mold travels in passing through the oven; the internal diameter of the mold; etc. However, when using a tubular mold having an internal diameter of 3 inches and an oven of such size that the mold must travel 10 feet in passing through the same and operating at an oven temperature of between 100 and 150 C., we nd that styrene may satisfactorily be charged into the mold at a constant rate of about 116 cubic centimeters per hour, thereby causing the mold to move to the left along track I3 at a rate of about 1 inch per hour. When using molds of larger diameter, slower lengthwise movement of the mold may be required.

As the mold moves to the left through the oven, additional mold sections are periodically assembled around the conduit 4 and are connected with the mold moving through the oven to form an extension Uf the same. Similarly, the portion of the mold emerging from the oven is permitted to cool by traveling a short distance therefrom,

- move into similar position away from the oven.

The portion of the polystyrene rod remaining within the mold seals the latter against leakage of the styrene which is -constantly pumped into the mold. The bubble-free polystyrene rod produced by this continuous polymerization method may be cut into any lengths desired. The rod is of uniform dameterland possesses a smooth nish.

It will be apparent that the invention is' not limited to the production of rod. By using a sectional mold similar in design and assemblage to that hereinbefore described, except that it has a square instead of circular bore, square bars of polymer may be produced. The sectional mold may also be designed so as to produce angles, I-beams, etc., as desired. By having suitable indentations on the inner surface of the mold sections, rods or bars, etc., having designs or other desired markings on their outer surface are readily produced.

It will alsobe apparent that changes may be made in the apparatus hereinbefore described Without departing from the invention. For instance, inrplace of the brake assemblage illustrated in the drawing, any means for applying a substantially constant force opposing the forward motion of the mold may be used. Such means may consist of a. frictionshoe applied against the outer surface ofthe mold, etc.

Y As hereinbefore pointed out, the method and apparatus disclosed may be used to prepare rods or other lengthy articles from any liquid organic compound which is readily polymerized by heat tov.a glass-like solid, and they are particularly well adapted to the production of such articles from vinyl aromatic compounds and their mixtures with other unsaturated organic compounds which co-polymerize therewith.

Other modes of applying the principle of the invention may be employed instead of those explained, change being made as regards the method -heren disclosed, provided thel step or steps'stated by any of the following claims or the equivalent of such stated step or steps be employed.

I therefore particularly point out and disy tinctly claim as my invention:

1. A'method for the continuous polymerization of polymerizable organic compounds to produce elongated solid articles of desired length which comprises introducing a liquid polymerizable organic compound under pressure at a fixed position into an elongated movable sectional container in such manner. as to cause the container merize the liquid organic compound and thence into a cooler zone wherein the polymer hardens while under the imposed pressure, and from time to time extending the walls of the container at a position preceding entrance of the latter into the heating zone and in a direction opposite the direction of movement of the container andremoving sections of the container from the hardened polymer.

2. A method for the continuous polymerization of styrene to produce elongated polystyrene articles of desired length which comprises introducing styrene under pressure at a fixed position into an elongated movable sectional container in such manner as to cause the container to move vgradually in a direction lengthwise of the container and away from said xed position by the force exerted thereon-by the liquid, exerting a force on the container to restrain the movement thereof so as to compress the charge therein` as a compact body substantially free of bubbles, causing the container in its lengthwise movement to travel slowly through a heating zone wherein it is heated sufficiently to polymerize the styrene and thence into a c oler zone wherein the polystyrene hardens w le under the imposed pressure, and from time to time extending the walls of the container at a position preceding entrance of the latter into the heating zone and in a direction opposite the direction of movement of the container and removing sections of the container from the hardened polystyrene.

DONALD L. GIBB. 

